Melt Processible Semicrystalline Fluoropolymer having Repeating Units Arising from Tetrafluoroethylene, Hexafluoropropylene, and Hydrocarbon Monomer Having a Carboxyl Group and a Polymerizable Carbon-Carbon Double Bond and Multi-Layer Articles Comprising a Layer of the Melt Processible Semicrystalline Fluoropolymer

Abstract

Disclosed is a melt processible semicrystalline fluoropolymer comprising: (a) about 2 to about 20 weight percent of repeating units arising from hexafluoropropylene; (b) about 0.001 to about 1 weight percent of repeating units arising from a hydrocarbon monomer having a carboxyl group and a polymerizable carbon-carbon double bond; and (c) the remaining weight percent of repeating units arising from tetrafluoroethylene. This melt processible semicrystalline fluoropolymer is impermeable to fuels and is useful as a lining for petroleum fuel tubing, as well as chemical resistance coating for, or adhesive between, perfluoropolymer and other polymers, metals and inorganics.

1 . A melt processible semicrystalline fluoropolymer comprising:
 (a) about 2 to about 20 weight percent of repeating units arising from hexafluoropropylene;   (b) from about 0.001 to about 1 weight percent of repeating units arising from a hydrocarbon monomer having a carboxyl group and a polymerizable carbon-carbon double bond; and   (c) the remaining weight percent of repeating units arising from tetrafluoroethylene.   
     
     
         2 . The melt processible semicrystalline fluoropolymer of  claim 1 , comprising:
 (a) about 2 to about 20 weight percent of repeating units arising from hexafluoropropylene;   (b) about 0.001 to about 1 weight percent of repeating units arising from a hydrocarbon monomer having a carboxyl group and a polymerizable carbon-carbon double bond;   (c) about 0.5 to about 10 weight percent of repeating units arising from perfluoro(alkyl vinyl ether); and   (d) the remaining weight percent of repeating units arising from tetrafluoroethylene; wherein the sum of the weight percent of repeating units arising from hexafluoropropylene and the weight percent of repeating units arising from perfluoro(alkyl vinyl ether) is greater than about 4 weight percent and less than about 20 weight percent.   
     
     
         3 . The melt processible semicrystalline fluoropolymer of  claim 1 , comprising:
 (a) about 4 to about 14 weight percent of repeating units arising from hexafluoropropylene;   (b) about 0.001 to about 1 weight percent of repeating units arising from a hydrocarbon monomer having a carboxyl group and a polymerizable carbon-carbon double bond and containing a dicarboxylic acid anhydride group or a dicarboxylic acid group;   (c) about 0.5 to about 3 weight percent of repeating units arising from perfluoro(alkyl vinyl ether); and   (d) the remaining weight percent of repeating units arising from tetrafluoroethylene.   
     
     
         4 . The melt processible semicrystalline fluoropolymer of  claims 1  or  2 , wherein said hydrocarbon monomer having a carboxyl group and a polymerizable carbon-carbon double bond contains a dicarboxylic acid anhydride group or a dicarboxylic acid group. 
     
     
         5 . A melt-blended mixture comprising a polymer and a melt processible semicrystalline fluoropolymer, wherein said melt processible semicrystalline fluoropolymer comprises:
 (a) about 2 to about 20 weight percent of repeating units arising from hexafluoropropylene;   (b) from about 0.001 to about 1 weight percent of repeating units arising from a hydrocarbon monomer having a carboxyl group and a polymerizable carbon-carbon double bond; and   (c) the remaining weight percent of repeating units arising from tetrafluoroethylene.   
     
     
         6 . A multi-layer article having a layer comprising a melt processible semicrystalline fluoropolymer, wherein said melt processible semicrystalline fluoropolymer comprises:
 (a) about 2 to about 20 weight percent of repeating units arising from hexafluoropropylene;   (b) from about 0.001 to about 1 weight percent of repeating units arising from a hydrocarbon monomer having a carboxyl group and a polymerizable carbon-carbon double bond; and   (c) the remaining weight percent of repeating units arising from tetrafluoroethylene.   
     
     
         7 . The multi-layer article of  claim 6 , comprising a layer of said melt processible semicrystalline fluoropolymer and a layer of substrate, and wherein the material comprising said layer of substrate contains a functional group that associates or bonds with the carboxyl group of said hydrocarbon monomer having a carboxyl group and a polymerizable carbon-carbon double bond. 
     
     
         8 . A multi-layer article comprising:
 (A) a first layer comprising at least one material selected from the group consisting of non-fluorinated polymer having polar functionality, metal and inorganic, and;   (B) a second layer comprising a melt processible semicrystalline fluoropolymer, wherein said melt processible semicrystalline fluoropolymer comprises:   (a) about 2 to about 20 weight percent of repeating units arising from hexafluoropropylene;   (b) about 0.001 to about 1 weight percent of repeating units arising from a hydrocarbon monomer having a carboxyl group and a polymerizable carbon-carbon double bond; and   (c) the remaining weight percent of repeating units arising from tetrafluoroethylene,   wherein (A) and (B) are in contiguous contact.   
     
     
         9 . The multi-layer article of  claim 8 , wherein said first layer comprises non-fluorinated polymer having polar functionality, and wherein said polar functionality is at least one selected from the group consisting of amine, amide, imide, nitrile, urethane, chloride, ether, ester, hydroxyl, carbonate and carboxyl. 
     
     
         10 . The multi-layer article of  claim 8 , wherein said non-fluorinated polymer having polar functionality is at least one selected from the group consisting of: ethylene-ethyl acrylate; ethylene-methyl acrylate; polyethylene-vinyl alcohol copolymers; polyamide; polyethylene terephthalate; polyimide; polymethyl methacrylate; polyvinyl acetate; polyvinyl alcohol, polycarbonate, polyvinyl butyral, polyurethane, polyacrylonitrile, and polyvinyl chloride. 
     
     
         11 . The multi-layer article of  claim 8 , wherein said first layer comprises metal, and wherein said metal is selected from the group consisting of aluminum, chromium, cobalt, copper, iron, manganese, molybdenum, nickel, niobium, rhenium, steel, tantalum, titanium, tungsten, and zirconium. 
     
     
         12 . The multi-layer article of  claim 8 , wherein said first layer comprise inorganic, and wherein said inorganic is selected from the group consisting of silicates, carbonates, sulfates, halides, oxides and sulfides. 
     
     
         13 . The multi-layer article of  claim 8 , wherein delamination does not occur below the yield strength of said first layer (A) and/or said second layer (B). 
     
     
         14 . The multi-layer article of  claim 8 , wherein said first layer comprises metal, and wherein the peel strength of said multi-layer article is greater than about 50 g/in. 
     
     
         15 . The multi-layer article of  claim 8 , further comprising a third layer (B1) comprising perfluoropolymer, wherein said third layer (B1) is in contiguous contact with said second layer (B). 
     
     
         16 . The multi-layer article of  claim 8 , wherein said multi-layer article is a multi-layer tube comprising:
 (A) a first layer comprising said non-fluorinated polymer having polar functionality, and in contiguous contact therewith;   (B) a second layer comprising said melt processible semicrystalline fluoropolymer;   wherein the layers are arranged concentrically such that said first layer (A) is outside of said second layer (B) and the outer face of said second layer (B) is in contiguous contact with the inner face of said first layer (A).   
     
     
         17 . The multi-layer article of  claim 16 , wherein said melt processible semicrystalline fluoropolymer has a CE10 fuel vapor transmission rate at 40° C. as measured by the procedure described in SAE J2659-03 of not greater than about 0.1 g·mm/m 2 ·day. 
     
     
         18 . The multi-layer article of  claim 16 , further comprising a third layer (B1) comprising perfluoropolymer, wherein the layers are arranged concentrically such that said third layer (B1) is inside of said second layer (B), and the outer face of said third layer (B1) is in contiguous contact with the inner face of said second layer (B). 
     
     
         19 . The multi-layer article of  claim 8 , wherein said multi-layer article is an insulated wire comprising:
 (A) a wire comprising metal; and   (B) a layer comprising said melt processible semicrystalline fluoropolymer;   wherein (A) and (B) are in contiguous contact.   
     
     
         20 . The multi-layer article of  claim 8 , wherein said multi-layer article is a melt extrusion die comprising metal having a flow passage coated with a composition comprising said melt processible semicrystalline fluoropolymer. 
     
     
         21 . The multi-layer article of  claim 8 , wherein said multi-layer article is an optical fiber comprising:
 (A) a fiber comprising an inorganic substrate; and   (B) a layer comprising said melt processible semicrystalline fluoropolymer;   wherein (A) and (B) are in contiguous contact.